AU600959B2 - 5-iminomethyl-haloacyloxazolidine having an inhibiting action on the phytotoxicity of herbicides - Google Patents
5-iminomethyl-haloacyloxazolidine having an inhibiting action on the phytotoxicity of herbicides Download PDFInfo
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- AU600959B2 AU600959B2 AU75932/87A AU7593287A AU600959B2 AU 600959 B2 AU600959 B2 AU 600959B2 AU 75932/87 A AU75932/87 A AU 75932/87A AU 7593287 A AU7593287 A AU 7593287A AU 600959 B2 AU600959 B2 AU 600959B2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
Abstract
Compounds of formula: <CHEM> where R is alkyl having from 1 to 8 carbon atoms, alkenyl, cyclohexyl or arylalkyl; R1 is alkyl having from 1 to 8 carbon atoms, alkenyl, cyclohexyl or arylalkyl; R and R1 being apt to form a -(CH2)-n group. These compounds can be used as phytotoxicity antidotes for thiolcarbamate and/or acetanilide herbicides for use on maize cultivations.
Description
COMMONWEALTH OF AUSTRALIA Form PATENTS ACT 1952 COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE Class Int. Class Application Number: Lodged: Complete Specification-Lodged: Accepted: Published: 'lis lc-'-I 'rm nt c 'I L i, amendnictits madc Ii-d' U'cin4laid sconr o Related Art: 1 Name of Applicant: SAddress of Applicant: TO BE COMPLETED BY APPLICANT OXON ITALIA S.P.A.
Via Sempione, 195 20016 Pero (Milano) Italy NELLO RONCHI SfANOERCOCK, SMITH BEADOLE 207 Riversdale R~oad, Box 410O) Hawthorn, Victoria, 3122 Actual Inventor: Address for Service: Complete Specification for the invention entitled: 5-IMIN0METHYL-HALOACYLOXA.0LIDINE HAVING AN INHIBITING ACTION ON THE PHYTOTOXICI'TY OF HERBICIDES The following statement is a full description of this invention, including the best method to me:of performing it known la There are known to be numerous thiolcarbamate and acetanilide herbicides which are highly effective against weeds infesting maize fields. However, these herbicides are frequently phycotoxic towards maize. On the other hand, those infesting weeds most difficult to destroy are not sufficiently controlled by herbicides which are less phytotoxic towards maize, as certain derivatives of the S-triazine or substituted urea families.
t C SIt is therefore very important to provide antidotes particularly effective in inhibiting the phytotoxicity of the thiolcarbamates and ace- Stanilides used as selective herbicides for maize.
It is known from literature that various classes of products having i this inhibiting action exist. Among the successfully tested compounds described in literature (EP 0021759, or British Patent 2043447) there are variously substituted haloacyloxazolidines.
The present invention relates to a haloacyloxazolidine family never t previously described in literature, namely dines, having the general formula: 00t t
R
CH CH CH N SCl 1 (I) SCH co- N 0 3 3 where R is alkyl having from 1 to 8 carbon atoms, alkenyl, cyclohexyl or arylalkyl1 R is alkyl having from 1 to 8 carbon atoms, alkenyl, cyclohexyl or arylalkyl; R and R I being apt to form a -(CH2)n group.
wherein n is an integer from 4 to 6, f :4~R Li! 1 -r These compounds are very effective as phytotoxicity antidotes or inhibitors both towards thiolcarbaiate herbicides, such as: di-pro pyl-S-e thyl- thiocarhamat e (EPTC) di-isobutyl-S-ethiyl-thiolcarbamate (Butylate) di-pro pyl-S-propyl-thiolcarbamate (Vernolate), and towards acetanilide herbicides, such as: 2-chloro-N-(ethoxymethyl)-2 -methyl-6 '-ethyl acetanilide (AC ETOCHLOR), 2-chiloro-N-(pyrazol-1-yl-methlyl)-', 61-dimethylacetanilide
(METAZACHLOR)
The compounds of formula according to the invention are synthe- C. sized in accordance with the following reactions: R R OH9 OH C H 2 01 N-OH 9 2 CH -CH -01l (II) 0RLRI
OH
The reaction 1) between epichlorhydria, and secondary amine is carried nut in L-5 hours, at a temperature of between 700 and 1000C, without the need to use solvents.
N 0I
R
2) N-OHI -OH-OHoc 0+ ROH 0 0 I) 0 R0 N-OH -CH-CH, -N Ri OH 0 0 The reaction 2) between compound (II) and potassium phthalimide is carried out in an alcohol at a temperature of between 650 and 8000, in 22 it 5-10 hours.
0 11 R 0 3) N CH CH CH N NH2-NH2.H20
ROH
I I 0
(IV)
0 R C
NH
/N -CH CH CH2 NH 2 LO R, OH
C
t The reaction 3) between compound (III) and hydrazine is carried out in an alcohol at a temperature of between 650 and 800C in 2-4 hours.
t R 0 4) N CH C C H NH CH -C CH 1/ 2 2 2 3 3 R1 OH
S(V)
t- ~R N -CH CH CH H 2 1 12 2 C3 \CH 3 3 The reaction 4) between compound (IV) and acetone is carried out by S azeotropic distillation of the water formed, using an organic solvent apt Z- to form an azeotrope with water.
R Cl 5) N CGH CH CH COC NaOH
R
I 0 NH Cl CH CH 3 -3 t -4-
R
N CH C CH Cl 2 2 R 0 N C CH NaC1 II C 0 Cl CH CH 3
(I)
3 3 The reaction 5) between compound and dichloracetyl 0o chloride is carried out in an organic solvent, normally that used in the preceding reaction in the presence of an acid 0o 0 o. acceptor (for example NaOH, KOH, and tertiary amines) at a oe« temperature of between -10° and +10°C in 15 minutes one hour.
The compounds of formula can be mixed with the aforesaid active herbicide substances to obtain new selective herbicide compositions for maize cultivations.
These herbicide compositions can also contain other aQ"-o selective maize herbicides such as S-triazine herbicides (for example atrazine, simazine, terbutylazine, cyanazine), substituted urea herbicides (for example linuron, metabenzthiazuron), dinitroaniline herbicides (for example pendimethalin), or other herbicides.
These herbicide compositions are obtained by mixing and possibly grinding the active substances with inert substances and adjuvants, and can be formulated either as wateremulsifiable liquids or as fluid suspensions (for example, water-based or organic solvent-based "flowables"). They can also be prepared in the form of granular compounds or as dry or wettable powders. The formulation methods for such herbicide 'A compositions are well known to the expert in the art, as are T mwspeOl3.oxon 90 5 18 NT C *,I v Li 4a the type of inert substances (liquids or solids) to be used and the various most suitable adjuvants.
The weight ratio between antidote compounds of formula (I) and active thiolcarbamate and/or acetabilide herbicide substances, phytotoxic to maize, can vary within very wide limits, but is generally between 1:1 and *t t t r t fr
I
rf tc S. r aft.
*4 1 4 0
S
S I It
I
-K
mwspeOl3.oxon 90 5 2 i4 c~ 2r 1
A
1:160 Herbicide compositions containing compounds of formula with thiolcarbamate and/or acetanilide herbicides can be used before sowing the maize, generally by incorporation into the soil by means of suitable equipment, whereas herbicide compositions containing compounds of formula and herbicide acetabilides can also be used on the soil surface after sowing the maize, without further incorporation, but being careful to use them within a few days from sowing (and anyhow before birth of the infesting weeds, i.e. at their initial appearance on the soil surface).
The aforesaid herbicide compositions are distributed over maize fields by suitable equipment, so as to generally apply a total quantity of herbicides plus antidotes, which may vary 0 0 o° from 1 to 17 kg of active substances per hectare.
S' A further method of application of the antidote compounds of formula is to treat maize seeds before sowing, and then o sowing the seeds treated with antidote compounds in fields which have already been deweeded with phytotoxic thiolcarbamate and/or acetanilide herbicides, or in fields which are to be deweeded, after sowing, with phytotoxic acetanilide herbicides.
If used for seed treatment, the compounds of formula (I) are formulated in suitable liquid, fluid or powder compositions ooo comprising active substances mixed with inert liquids or solids and/or adjuvants, well known to experts in the art, the compositions containing from 1 to 99% by weight of active substances.
The preparations obtained in this manner are applied to the o*:o seeds by standard equipment available in agriculture, using *4o4 S from 12.5 grams to 400 grams of antidotes per 100 kg of seeds.
The examples given hereinafter allow to better illustrate the invention, but without limiting it in any way.
PREPARATION EXAMPLE 1 Preparation of 2.2-dimethyl-N-dichloracetyl-5-diisobutylamino methyl oxazolidine ~w mwspe013/oxon 90 6 13 1 129.2 g of diisobutylamine are reacted for 3 hours at 800C with 101.7 g of epichlorhydrin.
After purifying by distillation, 199.5 g of N-(3-chloro-2-ol) propyl diisobutylamire are obtained. This product is then reacted at 800C for hours with 166.5 g of potassium phthalimide in 450 ml of anhydrous ethanol. After filtering off the formed potassium chloride, the mass is concentrated and left to crystallize.
261 g of N-(3-diisobutylamino-2-olpropyl) phthalimide are obtained.
The product obtained is hydrolysed by reaction for 3 hours at 800C in 1600 ml of ethanol with 44.1 g of hydrazine monohydrate.
After acidification with hydrochloric acid, the ethyl alcohol is distilled off, adding water. The phthalhydrazide is separated by filtration. The 3-diisobutyl-2-ol-propylamine is recovered from the mother liquors by alkalising with NaOH and extracting with toluene.
After drying the toluenic mass, 91 g of acetone are added and the mixture is heated to boiling, azeotropically distilling off the water formed in the reaction.
V c ,c tt 0 0 In this manner a toluenic solution of 0,2-dimethyl-5-diisobutylaminomethyl oxazolidine is obtained, which is reacted with 121 g of 20 dichloroacetylchloride and 110 g of 30% NaOH, at 0-50C, for 30 minutes.
Water is added to dissolve the sodium chloride formed. The organic layer is separated from the aqueous layer, and the solvent is removed by distillation to obtain 235 g of 2,2-dimethyl-3-dichloroacetyl-5-diisobutylamino methyl oxazolidine, in the form of a yellow-brown oil partially solid at ambient temperature.
The IR, NMR, elementary and gas chromatography analyses have confirmed the structure of the product obtained. This product is indicated hereinafter by the code number 0134.
PREPARATION EXAMPLES 2-9 The following products were synthesized using the method described in Example 1: 2,2-dimethyl-3-dichloroacetyl-5-ethyl cyclohexylamino methyl oxazo- 6 c
A
lidine 200.1 g obtained (code number: 0 135) 2,2-dimethyl-3-dichloroacetyl-5-dimethylamino methyl oxazolidine 248.5 g obtained (code number: 0 170) 2,2-dimethyl-3-dichloroacetyl-5-di-n-octylamino methyl oxazolidine 283.8 g obtained (code number: 0 171) 2,2-dimethyl-3-dichloroacetyl-5-di-n-propylamino methyl oxazolidine 139.8 g obtained (code number: 0 187) 2,2-dimethyl-3-dichloroacetyl-5-di-sec-butylamino methyl oxazolidine 215.4 g obtained (code number: 0 182) 2,2-dimethyl-3-dichloroacetyl-5-diallylamino methyl oxazolidine 77.04 g obtained (code number: 0 186) FORMULATION EXAMPLE 1 The following substances are mixed together in a liquid mixer: Technical EPTC 95% 758 g Technical 0 134 95% 63 g SOITEM* 115 100 g Solvent naphtha to make up to 1 litre A water-emulsifiable liquid is obtained, suitable for use as a S 20 herbicide in maize fields, for pre-sowing application by incorporation into the soil.
Emulsifier produced by SOITEM Milan a FORMULATION EXAMPLE 2 The following substances are mixed together: Technical butylate 96% 750 g Technical 0 134 95% 32 g SOGERONOL- FF4E 75 g Solvent naphtha to make up to 1 litre A water-emulsifiable liquid herbicide composition is obtained, for pre-sowing application to maize fields by incorporation.
i Emulsifier produced by GERONAZZO Milan FORMULATION EXAMPLE 3 7 7 f The following substances are mixed together: Technical acetochlor 95% 532 g Technical 0 134 95% 53 g SCITEM- 999 20 g SOITEM* 101 30 g monochlorobenzene to make up to 1 litre A water-emulsifiable liquid herbicide is obtained for pre-sowing or post-sowing application, but before appearance of infesting weeds on maize fields.
Emulsifiers produced by SOITEM Milan FORMULATION EXAMPLE 4 The following are mixed together: Technical 0 134 95% 263 g GERONOL* FF4E 100 g 15 xylol to make up to 1 litre Emulsifier produced by GERONAZZO Milan A water-emulsifiable liquid is obtained, which can be used for seed treatment.
Analogous compositions can be obtained using the compounds of Preparation Examples 2-9.
APPLICATION EXAMPLE 1 Aqueous emulsions of the herbicides ind-. ated in the following Table oo A are distributed over plastic bowls containing sandy loam soil, the emulsions being mixed before use with aqueous emulsions of compounds of formula prepared in accordance with the preceding Formulation Examples, the quantities being widely varied.
After distributing the mixtures of herbicides and compounds of formula these products are incorporated by being mixed with the soil to a depth of 10 cm.
ALBION maize is then sown together with infesting weed seeds, the bowls being then kept in a greenhouse at temperatures suited for maize and weed growth, irrigating every two days.
8 days after sowing, one observes the phytotoxicity level on the maize and weed growths emerging from the soil, said level being considered by the E.W.R.S. (European Weed Research Society) scale, as follows: Level 1 no phytotoxicity, healthy plants 2 about 2.5% phytotoxicity 3 about 5% phytotoxicity 4 about 10% phytotoxicity 5 about 15% phytotoxicity 6 about 25% phytotoxicity 7 about 35% phytotoxicity 8 about 62.5% phytotoxicity 9 plants totally destroyed.
In the following Table A, the infesting weeds considered are: 1. Echinochloa crus galli 2. Setaria viridis 3. Amaranthus retroflexus 4. Chenopodium album TABLE A Results of phytotoxicity levels 1-9, observed 30 days after sowing by the E.W.R.S. method on ALBION maize and various infesting weeds sown on soil treated with various mixtures of herbicides and compounds of formula Herbicide Quantity Compound Quantity Phytotoxicity 1-9 E.W.R.S.
Maize Infesting weeds _kg/ha form. I kg/ha 1_1. 2. 3. 4.
r
'I
C
rCr *6* 0O*
EPTC
EPTC
II
0 134
II
II
0 135 11 -9r~ 1 -1 b-o~nc~~ 49 99 o 9 o99 9 99" 15 9*9 99 9o So 99 7 TABLE A (continued) Herbicide Quantity CoMpound Quantity Phytotoxicity L-9 E.W.R.S.
Maize Infesting weeds k__/ha formi. I kg/ha 1. 2. 3. 4.
16+ 0.1 3 9 9 9 9 EPTC i6t 0187 1.6 1 9 9 9 9 16+ 0.4 2 9 9 9 9 16+ 0.1 3 9 9 9 9 EPTC 16 8 9 9 9 9 EPTC 8+ 0 134 1..6 1 9 9 9 9 8+ 0.4 1 9 9 9 9 8+ 0.1 1 9 9 9 9 EPTC 8+ 0 135 1.6 1 9 9 9 9 8+ 11 0.4 1 9 9 9 9 8+ it 0.1 2 9 9 9 9 EPTC 8+ 0 187 1.6 1 9 9 9 9 8+ I 0.4 1 9 9 9 9 8+ 0.1 2 9 9 9 9 EPTC 8 7 9 9 9 9 BUTYLATE 8+ 0 134 1.6 1 9 9 9 9 8+ 0.4 1 9 9 9 9 i 8+ 0.1 1 9 9 9 9 BUTYLATE 8+ 0 135 1.6 1 9 9 9 9 8+ 0.4 1 9 9 9 9 8+ 0.1 1 9 9 9 9 BUTYLATE 8+ 0 187 t.6 1 9 9 9 9 8+ 0.4 1 9 9 9 9 8+ 0.1 1 9 9 9 9 BUTYLATE 8 5 9 9 9 9 VERNOLATE 8+ 0 134 1.6 1 9 9 9 9 8+ 1 0.4 1 9 9 9 9 84-+it 0.1 2 9 9 9 9 VERNOLATE 8 6 9 9 9 9 99 0s 99 9 ACETOCHLOR 0 134 1 .6 0.4 0.1 10 rm~ 2 25 TABLE A (continued
I
Herbicide Quantity Compound form. I Quantity Phytoi Maize kr/ha toxicity 1-9 E.W.R.S.
Infesting weeds 1 9 ,1 ACETOCHLOR 4+ 0 135 1.6 1 9 9 9 9 4+ 0.4 3 9 9 9 9 4+ 0.1 4 9 9 9 9 ACETOCHLOR 4+ 0 187 1.6 2 9 9 9 9 4+ 0.4 2 9 9 9 9 4+ 0.1 4 9 9 9 9 ACETOCHLOR 4 6 9 9 9 9 ACETOCHLOR 2+ 0 134 1.6 1 9 9 9 9 2+ 0.4 1 9 9 9 9 2+ 0.1 2 9 9 9 9 ACETOCHLOR 2+ 0 135 1.6 2 9 9 9 9 2+ 0.4 3 9 9 9 9 2+ 0.1 3 9 9 9 9 ACETOCHLOR 2+ 0 187 1.6 1 9 9 9 9 2+ 0.4 2 9 9 9 9 2+ 0.1 3 9 9 9 9 ACETOCHLO 2 5 9 9 9 9 Untreated blank sample- 1 1 1 1 1 The results reported in Table formula compounds with herbici towards maize when not containing t A clearly indicate that mixtures of des, which are normally phytotoxic he formula compounds, eliminate maize phytotoxicity or reduce it to negligible levels, without reducing effectiveness towards weeds.
APPLICATION EXAMPLE 2 In plastic bowls containing sandy loam soil kept in a greenhouse and irrigated every two days one sows maize of the DEKALB XL 69 variety and seeds of various infesting weeds, and the next day the soil surface is sprayed with mixtures of aqueous acetochlor emulsions and aqueous emulsions of formula compounds, prepared in accordance with the preceding Formulation Examples, the quantities being widely varied.
days after sowing, the phytotoxicity 1-9 towards maize and 11 iJ' infesting weeds is considered by the E.W.R.S. method (as described in detail in the preceding example). The results observed are reported in the following Table B, in which the compound code numbers have the same meaning as in the preceding Table A.
TABLE B Phytotoxicity 1-9 considered by the E.W.R.S. method 30 days after sowing, having used herbicide compounds one day after sowing.
mixtures of acetochlor and formula (I) t 4-~ t I S 1 4 1 a a Herbicide Quantity Compound Quantity Phytotoxicity 1-9 E.W.R.S.
Maize Infesting weeds kg/ha form. 1 kg/ha 1. 2. 3. 4.
ACET0CHLOR 2+ 0 134 1.6 1 9 9 9 9 2-i I 0.4 1 9 9 9 9 2+ 0.1 3 9 9 9 9 ACET0CHL0R 2+ 0 135 1.6 1 9 9 9 9 2+ 0.4 2 9 9 9 9 2+ 0.1 4 9 9 9 9 AGET0CHLOR 2+ 0 187 1.6 1 9 9 9 9 2+ 0.4 1 9 9 9 9 2+ 0.1 3 9 9 9 9 ACETOCHLOR 2 6 9 9 9 9 ACETOCHLOR 1+i 0 134 1.6 1 9 9 9 9 1+ 11 0.4 1 9 9 9 9 1+ It0.1 1 9 9 9 9 ACETOCH-LOR 1+ 0 135 1.6 1 9 9 9 9 1+ 110.4 1 9 9 9 9 1+ it 0.1 3 9 9 9 9 ACETOCHLOR 1+ 0 187 1.6 1 9 9 9 9 1+i 0.4 1 9 9 9 9 1+ 0.1 2 9 9 9 9 ACET0CHL0R 5 9 9 9 9 12
II
TABI
(cmI
*C
4 *C I t ft
*CC
ft f 4.
ft ,E B Itinued) Herbicide Quantity Compound Quantity Phytotoxicity 1-9 E.W.R.S.
Maize Infesting weeds k_/ha form. I kg/ha 1. 2. 3. 4.
METAZACHLOR 1i 0 134 1.6 1 9 9 9 9 1+ 0.4 1 9 9 9 9 1+ 0.1 2 9 9 9 9 METAZACHLOR 6 9 9 9 9 The results reported in Table B clearly irdicate that compounds of formula eliminate phytotoxicity of ACETOCHLOR or reduce it to negligible levels when used after sowing, but before appearance of the maize and infesting weeds, without reducing the effectiveness of the herbicide towards weeds.
APPLICATION EXAMPLE 3 Aqueous emulsions of herbicides phytotoxic towards maize are 15 distributed in various quantities as reported in the following Table C over plastic bowls containing sandy loam soil, in which infesting weed seeds have been placed, said herbicides being then incorporated into the soil to a depth of 10 cm.
Maize seeds of the ISCHIA variety are separately treated with aqueous emulsions of formula compounds, prepared as indicated in the preceding Formulation Examples, using decreasing quantities of compounds per weight unit of seeds.
These seeds, treated with antidote compounds, are sown in the bowls treated with the various herbicides, and the phytotoxicity 1-9 towards maize and weeds is considered after 30 days by the E.W.R.S. method (as described in detail in Application Example 1).
The results observed are reported in the following Table C, in which the compound code numbers have the same meaning as in Tables A and B.
TABLE C Phytotoxicity 1-9 considered by the E.W.R.S. method, 30 days after sowing, using herbicide mixtures of acetochlor and formula compounds one day after sowing.
13
IS
I 1 Herbicide Quantity Compound Quantity Phytoto Maize -kg/hia form. I kg/.ha
EPTO
11
EPTC
EPTC
if I-r r 4r
C
EPTO
EPTC
It *1
C.
C
I C iC *4 a a Od I 0 £0S0 *4*0)4
A
EPTC
EPTC
11 16+ 16+ 16± 16+ 16+ 16+ 16+ 16± 16+ 86+ 8+ 8+ 8+ 8+ 8+ 8+ 8+ 8+ 8+ 8± 8+ 8+ 8+ 8+ 8+ 8+ 8+ 8+ o 134 o 135 o 187 o 134 11 0 135 11 0.4 0.2 0.05 0.0125 0.2 0.05 0.0125 0.2 0.05 0.0 125 0.2 0.05 0. 0125 0.2 0.05 0. 0125 0.2 0 .05 0.0125 2 3 1 2 4 8 14 xicity 1-9 E.W.R.S.
Infesting weeds 1. 2. 3. 4.
9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 it 0 187 11
EPTC
BUTYLATE
11 0 134 11 11
BUTYLATE
BUTYLATE
BUTYLATE
11 0 135 11 0.2 0.05 0. 0125 0.2 0.05 0.0125 0.2 0.05 0.0125 11 0 187 14 :i
I
i TABLE C (continued) Herbicide Quantity kg/ha
I
Compound Quantity Phytotoxicity 1-9 E.W.R.S.
Maize Infesting weeds form. I kg/ha 1. 2. 3. 4.
0 134 0.2 1 9 9 9 9 0.05 1 9 9 9 9 0.0125 2 9 9 9 9
VERNOLATE
ERNOLATE
V ERNOLATE r te
I
rl ri c t ti r r
I
r rr
ACETOCHLOR
II
II
ACETOCHLOR
It It
ACETOCHLOR
ACETOCHLOR
ACETOCHLOR
II
ACETOCHLOR
ACETOCHOR
ACETOCHLOR
II
II
ACETOCHLOR.
4+ 4+ 4+ 4+ 4+ 4+ 4+ 4+ 4+ 4+ 4 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2 2 0 134
II
i
II
II
0 135 II ii 0 187 0 134 It
II
0 135
II
0 187 i i
II
0.4 0.2 0.05 0.0125 0.2 0.05 0.0125 0.2 0.05 0.0125 0.2 0.05 0.0125 0.2 0.05 0.0125 0.2 0.05 0.0125 J f 4 t4J The results reported in Table C clearly indicate that the compounds of formula when applied directly to maize seeds, eliminate or reduce to negligible levels the phytotoxicity of thiolcarbamate or acetanilide herbicides used before maize sowing and incorporated into the soil, without reducing their effectiveness towards weeds.
The claims form part of the disclosure of this specification.
15
A
Claims (2)
- 9. Er 9. CH 2 CH CH2 N ClC CH 3 CH 3 (I) I P 04 9 0~*0 where R is alkyl having from 1 to 8 carbon atoms, alkenyl, cyclohexyl or arylalkyl; R, is alkyl having from 1 to 8 carbon atoms, alkeny-l, cyclohexyl or arylalkyl; R and R, being apt to form a -(CH 2 group; characterised in that it is carried out in accordance with the following reactions: 1) CH 2 CH CH 2 Cl HN R R ~N CH 2 CH CH 2 Cl R, OH- (II) MWSPEO13/OXON9061 90 6 13 R 2) N CH CH CH Cl R OH 1 R N- CH 2 CH CH R/ 2 1 0 II K K 0 N KC1 (III) £4 t~ I r I I~t t C 44 C t~ It let t *4 (It 3) N CH -CH CH R 7 OH 1 /c NC Q C NH2-NH2.H20 4. o lIt 4* I I 44 .4 .4 4** 4 44 4. 4.44 *44444 4 R N CH 2 CH CH2 NH 2 R H 2 R 1 0 C .H C (IV) R 4) N CH CH CH 2 NH 2 R OH 1 0 CH 3 CH R N CH 2 CH CH 2 R 0 H 1 CH3 CH 3 I-1- r, s T ~m. 18 R N CH 2 CH CH 2 R i 0 NH HCH CH3 CH3 CH COC1 NaOH Cl (I) I. e o o t If *I ft I o a r I o a o *61! I loot I II.I S* I a II< 0 0 I i R N- CH 2 CH CH 2 Cl RI 0 N C CH NaCI H 2 0 Ir \C C. 0 ^\C1 CH 3 CH 3 wherein n is an integer from 4 to 6 3) A synthesis method as claimed in claim wherein the reaction 1) between epichlorhydrin and secondary amine is carried out in 1-5 hours, at a temperature of between 70° and 100oC, without the need to use solvents. 4) A synthesis method as claimed in claim wherein the reaction 2) between compound (II) and potassium phthalimide is carried out in an alcohol at a temperature of between 65. and
- 80.C, in 5-10 hours. 5) A synthesis method as claimed in claim wherein the reaction 3) between compound (III) and hydrazine is carried out in an alcohol-at a temperature of between 65. and 80°C, in 2-4 hours. 6) A synthesis method as claimed in claim wherein the reaction 4) between compound (IV) and acetone is carried out by azeotropic distillation of the water formed, using an organic solvent apt to form an azeotrope with water. 7) A synthesis method as claimed in claim wherein the reaction 5) between compound and dichloracetyl chloride is mwspe01l/oxon 90 6 13 T 1 i -~lp l- I~_l l31 l~ la~lll~---C~---ilF1~ 18a- carried out in an organic solvent, normally that used in the preceding reaction 4) in the presence of an acid acceptor, for example NaOH, KOH, and tertiary amines at a temperature varying between -100 and +10 0 C, in 15 minutes 7 one hour. 8) A selective herbicide composition for maize, containing compounds of formula: A ii it IP *r 1 41 .4 I s Ii II I I I IC I I mwspe013.oxon 90 5 2 2'- R CH CH CH, N 2 2 Cl R CH C N 0 Cl CH CH 3 3 where R is alkyl having from 1 to 8 carbon atoms, alkenyl, cyclohexyl or arylalkyl 3 R is alkyl having from 1 to 8 carbon atoms, alkenyl, cyclohexyl or arylalkyl3 R and R being apt to form a -(CH group; together with thiolcarbamate and/or acetanilide herbicides and inert substances, wherein n is an integer from 4 to 6. 9) A composition as claimed in claim wherein the compound of formula is 2,2-dimethyl-3-dichloroacetyl-5-diisobutylamino methyl oxazolidine, and the herbicide is di-propyl-S-ethyl-thiolcarbamate. A composition as claimed in claim wherein the compound of formula is 2,2-dimethyl-3-dicnloroacetyl-5-diisobutylamino methyl oxazolidine, and the herbicide is di-isobutyl-S-ethyl-thiolcarbamate. 11) A composition as claimed in claim wherein the compound of formula is 2,2-dimethyl-3-dichloroacetyl-5-diisobutylamino methyl oxazolidine, and the herbicide is 2-chloro-N-(ethoxymethyl)-2'-methyl-6'- ethyl acetanilide. 12) A composition as claimed in claim wherein the weight ratio between compounds of formula and thiolcarbamate and/or acetanilide herbicides is between 1:1 and 1:160. 13) A method for the selective deweeding of maize cultivations, consisting in using in quantities varying from 1 to 17 kg/ha of active substances a herbicide composition containing compounds of formula: ii lit I 1;~ R CH CH CH 2 N S2 2 Cl CH CO N 0 1/ CH 3 3 R 1 19 -j 'i j where R is alkyl having from 1 to 8 carbon atoms, alkenyl, cyclohexyl or arylalkyl, R, is alkyl having from 1 to 8 carbon atoms, alkenyl, cyclohexyl or arylalkyl; R and R, being apt to form a -(CH 2 group; together with thiolcarbamate and/or acetanilide herbicides and inert substances, wherein n is an integer from 4 to 6. 14)A maize seed treatment composition, containing from 1 to 99% by weight of the compounds of formula claimed in claim 4 4 t I 4 4 c t 4 444 4 1). 15)A method for deweeding maize fields by using thiolcarbamate and/or acetanilide herbicides which are phytotoxic towards maize, together with maize seeds treated with antidote compounds of formula as claimed in claims 8) and/or 14), in quantities of between 12.5g and 400g per 100kg of seeds. 16)A method of synthesizing compounds or of deweeding maize or a compound or composition substantially as hereinbefore described with reference to any one of the Examples. DATED this 2 May, 1990 SMITH SHELSTON BEADLE Fellows Institute of Patent Attorneys of Australia Patent Attorneys for the Applicant: OXON ITALIA S.P.A. C C. mwspe0l3.oxon 90 5 2
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT21152/86A IT1196507B (en) | 1986-07-16 | 1986-07-16 | 5-IMMINOMETHYL-HACACOXYZOLIDONE AS INHIBITIVE ACTION OF HERBICIDE PHYTO-TOXICITY |
| IT21152/86 | 1986-07-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU7593287A AU7593287A (en) | 1988-01-21 |
| AU600959B2 true AU600959B2 (en) | 1990-08-30 |
Family
ID=11177516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU75932/87A Ceased AU600959B2 (en) | 1986-07-16 | 1987-07-16 | 5-iminomethyl-haloacyloxazolidine having an inhibiting action on the phytotoxicity of herbicides |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US4900350A (en) |
| EP (1) | EP0253291B1 (en) |
| JP (1) | JPS6360976A (en) |
| AT (1) | ATE67993T1 (en) |
| AU (1) | AU600959B2 (en) |
| BR (1) | BR8703692A (en) |
| DE (1) | DE3773441D1 (en) |
| DK (1) | DK371887A (en) |
| ES (1) | ES2025102B3 (en) |
| GR (1) | GR3003442T3 (en) |
| IL (1) | IL83210A (en) |
| IT (1) | IT1196507B (en) |
| PT (1) | PT85336B (en) |
| YU (1) | YU46217B (en) |
| ZA (1) | ZA875100B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1196507B (en) * | 1986-07-16 | 1988-11-16 | Oxon Italia Spa | 5-IMMINOMETHYL-HACACOXYZOLIDONE AS INHIBITIVE ACTION OF HERBICIDE PHYTO-TOXICITY |
| US5256626A (en) * | 1987-08-13 | 1993-10-26 | Monsanto Company | Herbicidal compositions safened by 5-heterocyclic-substituted oxazolidine dihaloacetamides compounds |
| US5691274A (en) * | 1990-12-12 | 1997-11-25 | Zeneca Limited | Antidoting herbicidal 3-isoxazolidinone compounds |
| US5527762A (en) * | 1990-12-12 | 1996-06-18 | Zeneca Limited | Antidoting herbicidal 3-isoxazolidinone compounds |
| US5395816A (en) * | 1990-12-12 | 1995-03-07 | Imperial Chemical Industries Plc | Antidoting herbicidal 3-ixoxazolidinone compounds |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2715631A (en) * | 1952-12-23 | 1955-08-16 | Rohm & Haas | Aminomethyloxazolidines |
| CA1014563A (en) * | 1972-10-13 | 1977-07-26 | Stauffer Chemical Company | Substituted oxazolidines and thiazolidines |
| US3959304A (en) * | 1974-07-01 | 1976-05-25 | Stauffer Chemical Company | Certain 3-haloacyl-2,2,5-trimethyl-oxazolidines |
| AR228034A1 (en) * | 1979-06-18 | 1983-01-14 | Stauffer Chemical Co | COMPOUNDS OF 3-ALCANOYL-5-METHYL SUBSTITUTED-OXAZOLIDINE AND HERBICIDE COMPOSITION THAT UNDERSTANDS IT AS AN ANTIDOTE |
| PL144076B1 (en) * | 1983-08-24 | 1988-04-30 | Stauffer Chemical Co | Herbicide |
| IT1196507B (en) * | 1986-07-16 | 1988-11-16 | Oxon Italia Spa | 5-IMMINOMETHYL-HACACOXYZOLIDONE AS INHIBITIVE ACTION OF HERBICIDE PHYTO-TOXICITY |
-
1986
- 1986-07-16 IT IT21152/86A patent/IT1196507B/en active
-
1987
- 1987-07-08 EP EP87109854A patent/EP0253291B1/en not_active Expired - Lifetime
- 1987-07-08 ES ES87109854T patent/ES2025102B3/en not_active Expired - Lifetime
- 1987-07-08 DE DE8787109854T patent/DE3773441D1/en not_active Expired - Fee Related
- 1987-07-08 AT AT87109854T patent/ATE67993T1/en not_active IP Right Cessation
- 1987-07-10 US US07/072,240 patent/US4900350A/en not_active Expired - Fee Related
- 1987-07-13 ZA ZA875100A patent/ZA875100B/en unknown
- 1987-07-15 BR BR8703692A patent/BR8703692A/en unknown
- 1987-07-16 YU YU133287A patent/YU46217B/en unknown
- 1987-07-16 JP JP62178140A patent/JPS6360976A/en active Pending
- 1987-07-16 IL IL83210A patent/IL83210A/en unknown
- 1987-07-16 AU AU75932/87A patent/AU600959B2/en not_active Ceased
- 1987-07-16 PT PT85336A patent/PT85336B/en not_active IP Right Cessation
- 1987-07-16 DK DK371887A patent/DK371887A/en not_active Application Discontinuation
-
1991
- 1991-12-27 GR GR91402182T patent/GR3003442T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK371887A (en) | 1988-01-17 |
| ES2025102B3 (en) | 1992-03-16 |
| JPS6360976A (en) | 1988-03-17 |
| US4900350A (en) | 1990-02-13 |
| ATE67993T1 (en) | 1991-10-15 |
| DK371887D0 (en) | 1987-07-16 |
| IL83210A0 (en) | 1987-12-31 |
| EP0253291A1 (en) | 1988-01-20 |
| EP0253291B1 (en) | 1991-10-02 |
| ZA875100B (en) | 1988-06-29 |
| GR3003442T3 (en) | 1993-02-17 |
| IT8621152A0 (en) | 1986-07-16 |
| YU133287A (en) | 1988-12-31 |
| YU46217B (en) | 1993-05-28 |
| PT85336B (en) | 1990-04-30 |
| IT1196507B (en) | 1988-11-16 |
| PT85336A (en) | 1987-08-01 |
| DE3773441D1 (en) | 1991-11-07 |
| IL83210A (en) | 1991-12-15 |
| AU7593287A (en) | 1988-01-21 |
| BR8703692A (en) | 1988-03-22 |
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